A cooperative catalysis approach for the asymmetric synthesis of succinates has been developed. The highly enantioselective <i>N</i>-heterocyclic carbene (NHC)-catalyzed β-protonation relies on the orchestration of three distinct organocatalysts, combining the unique reactivity of NHC-generated homoenolate equivalents with powerful H-bond donor and acyl transfer cocatalysts. This cooperative catalyst system enhances both yield and selectivity, compared to only the NHC-catalyzed process. The succinate products are of particular interest as they allow selective differentiation of the ester functionalities, facilitating transformations to chiral small molecule building blocks, including lactones and β-amino esters. This new method allows for the efficient conversion of a large scope of aryl-oxobutenoates to highly enantioenriched succinate derivatives and demonstrates the benefits of utilizing distinct activation modes in organocatalysis. This presentation will demonstrate the broad substrate scope for β-protonation as well as insights into the interactions of the cocatalysts.

Enantioselective β-protonation by a cooperative catalysis strategy

251st National Meeting (2016)

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